The Role of Alkyl Chains in the Thermoresponse of Supramolecular Network.

Supramolecular materials provide a pathway for achieving precise, highly ordered structures while exhibiting remarkable response to external stimuli, a characteristic not commonly found in covalently bonded materials. The design of self-assembled materials, where properties could be predicted/design from chemical nature of the individual building blocks, hinges upon our ability to relate macroscopic properties to individual building blocks - a feat which has thus far remained elusive. Here, a design approach is demonstrated to chemically engineer the thermal expansion coefficient of 2D supramolecular networks by over an order of magnitude (\boldmath 120 to \boldmath 1000 × 10-6 K-1). This systematic study provides a clear pathway on how to carefully design the thermal expansion coefficient of a 2D molecular assembly. Specifically, a linear relation has been identified between the length of decorating alkyl chains and the thermal expansion coefficient. Counter-intuitively, the shorter the chains the larger is the thermal expansion coefficient. This precise control over thermo-mechanical properties marks a significant leap forward in the de-novo design of advanced 2D materials. The possibility to chemically engineer their thermo-mechanical properties holds promise for innovations in sensors, actuators, and responsive materials across diverse fields.

Nonmonotonic Velocity Dependence of Atomic Friction Induced by Multiple Slips.

The transition from single to multiple atomic slips, theoretically expected and important in atomic-scale friction, has never been demonstrated experimentally as a function of velocity. Here we show by high-resolution friction force microscopy on monolayer MoS_{2}/Au(111) that multiple slips leave a unique footprint-a frictional velocity weakening. Specifically, in a wide velocity interval from 10 to 100 nm/s, friction surprisingly decreases. Model simulations show a similar nonmonotonic behavior at velocities in quantitative agreement with experiment. Results suggest a velocity-corrugation phase diagram, whose validity is proposed more generally.

Moiré-Tile Manipulation-Induced Friction Switch of Graphene on a Platinum Surface.

Friction control and technological advancement are intimately intertwined. Concomitantly, two-dimensional materials occupy a unique position for realizing quasi-frictionless contacts. However, the question arises of how to tune superlubric sliding. Drawing inspiration from twistronics, we propose to control superlubricity via moiré patterning. Friction force microscopy and molecular dynamics simulations unequivocally demonstrate a transition from a superlubric to dissipative sliding regime for different twist angles of graphene moirés on a Pt(111) surface triggered by the normal force. This follows from a novel mechanism at superlattice level where, beyond a critical load, moiré tiles are manipulated in a highly dissipative shear process connected to the twist angle. Importantly, the atomic detail of the dissipation associated with the moiré tile manipulation─i.e., enduring forced registry beyond a critical normal load─allows the bridging of disparate sliding regimes in a reversible manner, thus paving the road for a subtly intrinsic control of superlubricity.

Velocity Dependence of Moiré Friction.

Friction force microscopy experiments on moiré superstructures of graphene-coated platinum surfaces demonstrate that in addition to atomic stick-slip dynamics, a new dominant energy dissipation route emerges. The underlying mechanism, revealed by atomistic molecular dynamics simulations, is related to moiré ridge elastic deformations and subsequent relaxation due to the action of the pushing tip. The measured frictional velocity dependence displays two distinct regimes: (i) at low velocities, the friction force is small and nearly constant; and (ii) above some threshold, friction increases logarithmically with velocity. The threshold velocity, separating the two frictional regimes, decreases with increasing normal load and moiré superstructure period. Based on the measurements and simulation results, a phenomenological model is derived, allowing us to calculate friction under a wide range of room temperature experimental conditions (sliding velocities of 1-104 nm/s and a broad range of normal loads) and providing excellent agreement with experimental observations.

Flexible Superlubricity Unveiled in Sidewinding Motion of Individual Polymeric Chains.

A combination of low temperature atomic force microcopy and molecular dynamic simulations is used to demonstrate that soft designer molecules realize a sidewinding motion when dragged over a gold surface. Exploiting their longitudinal flexibility, pyrenylene chains are indeed able to lower diffusion energy barriers via on-surface directional locking and molecular strain. The resulting ultralow friction reaches values on the order of tens of pN reported so far only for rigid chains sliding on an incommensurate surface. Therefore, we demonstrate how molecular flexibility can be harnessed to realize complex nanomotion while retaining a superlubric character. This is in contrast with the paradigm guiding the design of most superlubric nanocontacts (mismatched rigid contacting surfaces).

Sequential Bending and Twisting around C-C Single Bonds by Mechanical Lifting of a Pre-Adsorbed Polymer.

Bending and twisting around carbon-carbon single bonds are ubiquitous in natural and synthetic polymers. Force-induced changes were so far not measured at the single-monomer level, owing to limited ways to apply local forces. We quantified down to the submolecular level the mechanical response within individual poly-pyrenylene chains upon their detachment from a gold surface with an atomic force microscope at 5 K. Computer simulations based on a dedicated force field reproduce the experimental traces and reveal symmetry-broken bent and rotated conformations of the sliding physisorbed segment besides steric hindrance of the just lifted monomer. Our study also shows that the tip-molecule bond remains intact but remarkably soft and links force variations to complex but well-defined conformational changes.

A Two-Dimensional Polymer Synthesized at the Air/Water Interface.

A trifunctional, partially fluorinated anthracene-substituted triptycene monomer was spread at an air/water interface into a monolayer, which was transformed into a long-range-ordered 2D polymer by irradiation with a standard UV lamp. The polymer was analyzed by Brewster angle microscopy, scanning tunneling microscopy measurements, and non-contact atomic force microscopy, which confirmed the generation of a network structure with lattice parameters that are virtually identical to a structural model network based on X-ray diffractometry of a closely related 2D polymer. The nc-AFM images highlight the long-range order over areas of at least 300×300 nm2 . As required for a 2D polymer, the pore sizes are monodisperse, except for the regions where the network is somewhat stretched because it spans over protrusions. Together with a previous report on the nature of the cross-links in this network, the structural information provided herein leaves no doubt that a 2D polymer has been synthesized under ambient conditions at an air/water interface.

Surface science at the PEARL beamline of the Swiss Light Source.

The Photo-Emission and Atomic Resolution Laboratory (PEARL) is a new soft X-ray beamline and surface science laboratory at the Swiss Light Source. PEARL is dedicated to the structural characterization of local bonding geometry at surfaces and interfaces of novel materials, in particular of molecular adsorbates, nanostructured surfaces, and surfaces of complex materials. The main experimental techniques are soft X-ray photoelectron spectroscopy, photoelectron diffraction, and scanning tunneling microscopy (STM). Photoelectron diffraction in angle-scanned mode measures bonding angles of atoms near the emitter atom, and thus allows the orientation of small molecules on a substrate to be determined. In energy scanned mode it measures the distance between the emitter and neighboring atoms; for example, between adsorbate and substrate. STM provides complementary, real-space information, and is particularly useful for comparing the sample quality with reference measurements. In this article, the key features and measured performance data of the beamline and the experimental station are presented. As scientific examples, the adsorbate-substrate distance in hexagonal boron nitride on Ni(111), surface quantum well states in a metal-organic network of dicyano-anthracene on Cu(111), and circular dichroism in the photoelectron diffraction of Cu(111) are discussed.

Nanostructuring of an alkali halide surface by low temperature plasma exposure.

Templating insulating surfaces at the nanoscale is an interesting prospect for applications that involve the adsorption of molecules or nanoparticles where electronic decoupling of the adsorbed species from the substrate is needed. In this study, we present a method to structure alkali halide surfaces at the nanoscale using a combination of low temperature plasma exposure and annealing, and characterize the surfaces by atomic force microscopy. We find that nanostructurating can be controlled by the duration of the exposure, the atomic mass of the plasma gas and the subsequent step-by-step annealing process. In contrast to previous studies with electron or high energy (few keV) ion irradiation, our approach of employing moderate particle energy (10-15 eV Ar+ or He+ ions) results in fine nanostructuring at length scales of nanometers and even single atom vacancies.

Quantifying the atomic-level mechanics of single long physisorbed molecular chains.

Individual in situ polymerized fluorene chains 10-100 nm long linked by C-C bonds are pulled vertically from an Au(111) substrate by the tip of a low-temperature atomic force microscope. The conformation of the selected chains is imaged before and after manipulation using scanning tunneling microscopy. The measured force gradient shows strong and periodic variations that correspond to the step-by-step detachment of individual fluorene repeat units. These variations persist at constant intensity until the entire polymer is completely removed from the surface. Calculations based on an extended Frenkel-Kontorova model reproduce the periodicity and magnitude of these features and allow us to relate them to the detachment force and desorption energy of the repeat units. The adsorbed part of the polymer slides easily along the surface during the pulling process, leading to only small oscillations as a result of the high stiffness of the fluorenes and of their length mismatch with respect to the substrate surface structure. A significant lateral force also is caused by the sequential detachment of individual units. The gained insight into the molecule-surface interactions during sliding and pulling should aid the design of mechanoresponsive nanosystems and devices.

Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO2 (110).

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

Ordered heteromolecular overlayers formed by metal phthalocyanines and porphyrins on rutile titanium dioxide surface studied at room temperature.

Molecular heterostructures are formed from meso-tetraphenyl porphyrins-Zn(II) (ZnTPP) and Cu(II)-phthalocyanines (CuPc) on the rutile TiO2(011) surface. We demonstrate that ZnTPP molecules form a quasi-ordered wetting layer with flat-lying molecules, which provides the support for growth of islands comprised of upright CuPc molecules. The incorporation of the ZnTPP layer and the growth of heterostructures increase the stability of the system and allow for room temperature scanning tunneling microscopy (STM) measurements, which is contrasted with unstable STM probing of only CuPc species on TiO2. We demonstrate that within the CuPc layer the molecules arrange in two phases and we identify molecular dimers as basic building blocks of the dominant structural phase.

Local detection of nitrogen-vacancy centers in a nanodiamond monolayer.

Nitrogen-vacancy defect centers (NV) contained in nanodiamonds (NDs) are a promising candidate in quantum information processing and single photon sources due to the capability of controlling their assembly on various surfaces. However, their detection with traditional optical techniques becomes challenging when probing high NV densities at the nanometer scale. Here, we combine scanning probe techniques to characterize in a monolayer the structural and electronic properties of bucky-diamonds with sizes below 10 nm. We further observe by light-assisted Kelvin- and scanning tunneling spectroscopy a clear signature of negatively charged subsurface NV centers in NDs at the nanoscale where conventional techniques are limited.

Probing charge redistribution at the interface of self-assembled cyclo-P5 pentamers on Ag(111).

Phosphorus pentamers (cyclo-P5) are unstable in nature but can be synthesized at the Ag(111) surface. Unlike monolayer black phosphorous, little is known about their electronic properties when in contact with metal electrodes, although this is crucial for future applications. Here, we characterize the atomic structure of cyclo-P5 assembled on Ag(111) using atomic force microscopy with functionalized tips and density functional theory. Combining force and tunneling spectroscopy, we find that a strong charge transfer induces an inward dipole moment at the cyclo-P5/Ag interface as well as the formation of an interface state. We probe the image potential states by field-effect resonant tunneling and quantify the increase of the local change of work function of 0.46 eV at the cyclo-P5 assembly. Our experimental approach suggest that the cyclo-P5/Ag interface has the characteristic ingredients of a p-type semiconductor-metal Schottky junction with potential applications in field-effect transistors, diodes, or solar cells.

Energy loss triggered by atomic-scale lateral force.

We perform bimodal atomic force microscopy measurements on a Br-doped NaCl (001) surface to investigate the mechanisms behind frequency shift and energy dissipation contrasts. The peculiar pattern of the dissipated energy in the torsional channel, related to frictional processes, is increased at the positions of Br impurities, otherwise indistinguishable from Cl ions in the other measured channels. Our simulations reveal how the energy dissipates by the rearrangement of the tip apex and how the process is ultimately governed by lateral forces. Even the slightest change in lateral forces, induced by the presence of a Br impurity, is enough to trigger the apex reconstruction more often, thus increasing the dissipation contrast; the predicted dissipation pattern and magnitude are in good quantitative agreement with the measurements.

Systematic study of the dolomite (104) surface by bimodal dynamic force microscopy in ultra-high vacuum.

We have investigated the morphology and structure of dolomite MgCa(CO(3))(2)(104) surfaces by bimodal dynamic force microscopy with flexural and torsional resonance modes in ultra-high vacuum at room temperature. We found that the surface slowly decomposes by degassing CO(2) in a vacuum and becomes covered by amorphous clusters, presumably MgO and CaO. By choosing an optimal sample preparation procedure (i.e. cleaving in a vacuum and mild annealing for stabilizing clusters for a short time), atomically clean surfaces were obtained. The complex tip-sample interaction, arising from carbonate groups and Mg and Ca atoms of the surface, induces a large variety of atomic-scale imaging features.

Strong signature of electron-vibration coupling in molecules on Ag(111) triggered by tip-gated discharging.

Electron-vibration coupling is of critical importance for the development of molecular electronics, spintronics, and quantum technologies, as it affects transport properties and spin dynamics. The control over charge-state transitions and subsequent molecular vibrations using scanning tunneling microscopy typically requires the use of a decoupling layer. Here we show the vibronic excitations of tetrabromotetraazapyrene (TBTAP) molecules directly adsorbed on Ag(111) into an orientational glassy phase. The electron-deficient TBTAP is singly-occupied by an electron donated from the substrate, resulting in a spin 1/2 state, which is confirmed by a Kondo resonance. The TBTAP•- discharge is controlled by tip-gating and leads to a series of peaks in scanning tunneling spectroscopy. These occurrences are explained by combining a double-barrier tunneling junction with a Franck-Condon model including molecular vibrational modes. This work demonstrates that suitable precursor design enables gate-dependent vibrational excitations of molecules on a metal, thereby providing a method to investigate electron-vibration coupling in molecular assemblies without a decoupling layer.

Solution-Synthesized Extended Graphene Nanoribbons Deposited by High-Vacuum Electrospray Deposition.

Solution-synthesized graphene nanoribbons (GNRs) facilitate various interesting structures and functionalities, like nonplanarity and thermolabile functional groups, that are not or not easily accessible by on-surface synthesis. Here, we show the successful high-vacuum electrospray deposition (HVESD) of well-elongated solution-synthesized GNRs on surfaces maintained in ultrahigh vacuum. We compare three distinct GNRs, a twisted nonplanar fjord-edged GNR, a methoxy-functionalized "cove"-type (or also called gulf) GNR, and a longer "cove"-type GNR both equipped with alkyl chains on Au(111). Nc-AFM measurements at room temperature with submolecular imaging combined with Raman spectroscopy allow us to characterize individual GNRs and confirm their chemical integrity. The fjord-GNR and methoxy-GNR are additionally deposited on nonmetallic HOPG and SiO2, and fjord-GNR is deposited on a KBr(001) surface, facilitating the study of GNRs on substrates, as of now not accessible by on-surface synthesis.

Measuring electric field induced subpicometer displacement of step edge ions.

We provide unambiguous evidence that the applied electrostatic field displaces step atoms of ionic crystal surfaces by subpicometers in different directions via the measurement of the lateral force interactions by bimodal dynamic force microscopy combined with multiscale theoretical simulations. Such a small imbalance in the electrostatic interaction of the shifted anion-cation ions leads to an extraordinary long-range feature potential variation and is now detectable with the extreme sensitivity of the bimodal detection.

Interplay of the tip-sample junction stability and image contrast reversal on a Cu(111) surface revealed by the 3D force field.

Non-contact atomic force microscopy is used to measure the 3D force field on a dense-packed Cu(111) surface. An unexpected image contrast reversal is observed as the tip is moved towards the surface, with atoms appearing first as bright spots, whereas hollow and bridge sites turn bright at smaller tip-sample distances. Computer modeling is used to elucidate the nature of the image contrast. We find that the contrast reversal is essentially a geometrical effect, which, unlike in gold, is observable in Cu due to an unusually large stability of the tip-sample junction over large distances.